Lubricants and lubricated structures



Oct. 18, 1966 L, 5 5T. P R ETAL 3,280,027

LUBRICANTS AND LUBRICATED STRUCTURES Filed Dec. 29, 1965 eww 5 NH .7. .e0 HW M6 0 m A M55 e e I w% Mo 6 L n United States Patent Ofihce3,289,027 Patented 001:. 18, 1966 3,280,027 LUBRICANTS AND LUBRICATEDSTRUCTURES Leon E. St. Pierre, St. Lambert, Quebec, (Ianada, and RobertS. Owens, Latham, N.Y., assignors to General Electric Company, acorporation of New York Filed Dec. 29, 1965, Ser. No. 522,014 30 Claims.(Cl. 252-45) This application is a continuation-in-part of our copendingapplication Serial No. 180,884, filed March 19, 1962, as acontinuation-in-part of our application Serial No. 101,917, filed April10, 1961, now abandoned, both of which are assigned to the assignee ofthe present application.

The present invention relates to improved lubricants and uses of thesematerials as lubricants for various contacting metallic surfaces,particularly aluminum surfaces. More particularly, the invention relatesto a new class of lubricants which are monoolefinic compounds containinga polar group and a long chain saturated aliphatic group. Theselubricants have been found to be especially useful in those cases wherenew metal surfaces are being created or where high wear is a problemparticularly in cases of boundary lubrication. These lubricants may beused either alone, or as emulsions, suspensions, for example, in aqueousmedia. They likewise may be used as additives in combination with otherwell known lubricating materials having the desired lubricatingviscosity such as mineral oils, silicone oils, diester lubricants, etc.,in the form of solutions, emulsions, suspensions, etc.

Attempts have been made in the past to effect lubrication of aluminumsurfaces. Thus, it has been desired to effect lubrication of relativelymoving surfaces in which one of the surfaces is a metal compositioncontaining at least 50% by weight aluminum, for instance, pure aluminum,alloys of aluminum,'etc. The lubrication of such aluminum surfaces isespecially diificult in cases Where extreme pressure conditions existrequiring lubrication under boundary conditions, i.e., actualsolid-to-solid contact, for instance, as may be found in a hearingbefore a hydrodynamic film of lubricant is created or where new solidsurfaces are being generated, for example, in shaping by drawing througha die, in cutting, for example, in a lathe or punch-press, in shaping,for example, by stamping, drawing, extrusion, spinning, cold-rolling, inpolishing, for example by lapping, burnishing, etc. For convenience,this type of lubrication is hereinafter referred to as boundarylubrication. Under such conditions, it has been found that aluminumcompositions are lubricated with great difficulty due to the fact thatunder extreme pressure conditions of boundary lubrication, the aluminumsurface tends to score, gall or seize, even when great care isexercised. To the best of our knowledge, no previous lubricant has beenknown which completely satisfies the requirements of boundarylubrication of aluminum metal compositions containing at least 50% byweight aluminum.

Unexpectedly, we have found that monoolefinic compounds in theunpolymerized, that is, the monomeric state, having a polar group or nomore than 4 carbon atoms removed from the olefinic groups, can be usedas lubricants between two solid surfaces which move relative to eachother, even under high pressure conditions, or may be used as additivesto other well known lubricants to impart improved boundary lubricatingcharacteristics to such lubricants, as, for instance, those mentionedabove, examples of which are mineral oils of lubricating viscosity,lubricating greases, silicone lubricating oils, diester lubricatingoils, polyester lubricants, silicate ester lubricants, etc. When thesemonoolefinic compounds are employed in lubricating the aluminum surfaceor surfaces, it is found that the coeflicient of friction is. greatlyreduced, and the tendency to gall or seize, particularly under boundarylubrication conditions, is materially reduced and in many instances iscompletely eliminated. Furthermore, it is found that in addition to theimproved lubricating characteristics of these monoolefinic compounds,the act of one surface moving across another surface in the presence ofthese monoolefinic compounds imparts a high polish to the aluminumsurface in many applications, thereby still further increasing the easewith which our lubricating compositions can contribute to thelubricating act.

In addition to our lubricating compositions being especially adaptablefor lubricating relatively moving surfaces at least one surface of whichis an aluminum surface, we have also found unexpectedly that theselubricating compositions are also useful in effecting improvedlubrication of other solid surfaces moving relative to each other,especially when one of these surfaces is a metal used for fabricatingstructural shapes, for example, iron, molybdenurn, silver, copper,beryllium, tungsten, magnesium, titanium, zirconium, chromium, nickel,cobalt, aluminum, tin, etc., and various metal compositions, forexample, alloys of the aforesaid metals, of which typical examples aresteels, brasses, the various alloys of magnesium, cobalt, zinc,zirconium, beryllium, iron (e.g., stainless steel), etc. The othersurface may be the same or different metal, or it may be another solidmaterial for example, wood, molded synthetic resins, laminates, etc., ora special compounded composition, such as, porous metal, graphite,graphite-impregnated metal, soft bearing alloys, e.g., babbitts, etc.,or very hard compositions, for example, metal carbides, nitrides, etc.

The fact that our monoolefinic compounds may be used as lubricants forthese various classes of materials and are particularly useful aslubricants under a wide variety of conditions for two solid surfacesmoving relative to each other where at least one of the surfaces iseither aluminum or an alloy of aluminum, was entirely unexpected and inno way could have ben predicted, because the prior art has been of theimpression that the usual lubricants and the usual lubricating materialsand techniques were not effective lubricants under many conditions forrelatively moving surfaces in which one of the surfaces was aluminum orone of its many alloys. This was due to the fact that aluminum and manyof its alloys are relatively soft and when the usual lubricants, evenextreme pressure lubricants containing additives to increase the loadbearing characteristics of the lubricant, are used for lubricating suchmaterials, undesirable wear, galling, and ultimate seizure of therelatively moving parts occurs. This is particularly borne out by arecent article by R. D. Guminski and J. Willis entitled Development ofCold-Rolling Lubricants for Aluminum Alloys, in Journal of the Instituteof Metals, 8 8, pages 481-492 (1960), where the authors point out theundesirability of having unsaturated additives as lubricants in thecoldrolling of aluminum alloys.

Our invention may be better understood from the following descriptiontaken in conjunction with the appended drawings, in which:

FIG. 1 shows, partly in section, the portion of a standard four-ballwear tester which has been modified to evaluate lubricating compositionsusing metals in various shapes other than balls;

FIG. 2 shows the bell housing, partly in section, of one end of anelectric motor cut away to show an aluminum sleeve bearing integrallycast as part of the bell housing; and

FIG. 3 'showns an end view of a portion of the bell housing of FIG. 2along line 3 3.

These new lubricants are monomeric compounds (hereinafter so designated)having the general formula and R" is a monovalent radical selected fromthe group consisting of linear alkyl radicals with from 11 to 60 carbonatoms, and linear fluoroalkyl radicals with from 11 to 60 carbon atoms.X and R" together represent the monovalent group -XR" which encompassesthe radicals where R is as previously defined.

In the foregoing general formula, the radical represented by is therepresentative of the following more specific formulae when n is 0, itrepresents the two radicals all and when n is 1, it is representative ofthe following three It will be recognized that when R is either hydrogenor fluorine, Formulae w and b represent the same radicals, and Formulaec, d and 2 also represent the same radicals. However, when R is methyl,or one of the three fluorornethyl radicals, all four formulae representdifferent radicals.

Typical of the radicals represented by Formulae a and b are, for examplevinyl, propeny'l, l-methylvinyl and the fluorine-substituted derivativesof these three hydrocarbon radicals, for exaxmple,

l-fluorovinyl,

1 ,2,2-trifluorovinyl, l-fiuoropropenyl, Z fiuorOpropenyl,3-fluo-ropropenyl, 3,3-difinoropropenyl, 3,3,3-trifluoropropenyl,l-(fiu-oromethyDvinyl,

1 -met'hyl-2 -fluorovinyl, 1-( difluoromethyl) vinyl, 1 trifiuoromethylvinyl, 1-(trifluoromethyl-Z,2-difluorovinyl), etc.

Typical of the radicals covered by Formulae c, d and e are, for exampleallyl, crotonyl, (Z-butenyl), isocrotonyl, (Z-isobutenyl),l-methylallyl, 2-methylallyl and the fluorine-substituted derivatives ofthese five hydrocarbon radicals, for example,

2- (trifiuoromethyl)-3,3-difluoroallyl, etc.

Typical examples of "radicals represented R" are the linear alkylradicals, e.g., undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl,octadecyl, nonadecyl, eicosyl, dicosyl, tri-cosyl, heptacosy-l,tr-iacontyl, dotriacontyl, tetrac-ontyl, pentaoontyl, hexacontyl, andthe fluorosubstituted derivatives of these hydrocarbons, in which one ormore, up to all, of the hydrogen atoms have been substituted by afluorine atom. Typical of the linear fluoroalkyl radicals are, by way ofexample, the mono, di-, tri-, tetra-, penta-, hexa-, up topentacosylfluorododecyl, the mono-, di-, tri-, tetra-, penta-, et-c., upto hentetracontylfluoroeicosyl, etc., radicals.

The compounds are monoolefinic alkyl ethers when X is oxygen;monoolefinic alkyl sulfides sometimes also known as thioethers, when Xis sulfur; monoolefinic alkyl ketones when X is carbonyl; monoole-finicalkyl carbonates when X is carbonate; monoolefinic alkyl sulfoxides whenX is sulfoxy; monoo'lefinic alkyl sulf-ones when X is sulfonyl; and maybe either the monoole-finic alcohol ester of an alkyl carboxylic acid,or an alkyl alcohol ester of a monoolefinic unsaturated carboxylic acidwhen X is carbony-loxy.

Typical examples of the various compounds falling within this generalformula are as follows:

Vinyl undecyl ether, vinyl undecyl sulfide, vinyl undecyl ketone, vinylundecyl carbonate, vinyl undecyl sulfoxide, vinyl undecyl sulfone,undecyl acrylate, vinyl laurate, vinyl tetradecyl ether, vinyl hexadecylether, v-i-nyl octadecyl ether, vinyl eicosyl ether, vinyl tricosylethe-r, vinyl hexacosyl ether, vinyl octacosyl ether, vinyl tri;

acontyl ether, vinyl dotriacontyl ether, vinyl tetracontyl ether, vinylpentacontyl ether, vinyl hexac-ontyl ether, 1- methylvinyl dodecylether, al-lyl dodecyl ether, Z-methylallyl dodecyl ether, isocrotenyldode-cyl ether, crotenyl dodecyl ether, allyl dodecyl sulfide,Z-methylallyl tetradecyl ketone, crotonyl hexadecyil carbonate,.isocrotonyl octadecyl sulfoxide, 2 methy-lallyl eicosyl sulfone,hexadecyl acrylate, dodecyl methacrylate, oc-tadecyl vinylacetate,eicosyl crotonate, tetradecyl isoerotonate, dodecyl angelate, tricontyltiglate, vinyl searate, vinyl palmitate, allyl stearate, methylallylpalmitate, crotonyl behanate, is-ocrotonyl cerotate, vinyl my-ristate,dodecyl vinylacetate, l-methylvinyl octadecyl sulfide, l-met-hylallyldocosyl ketone, allyl hexadecyl sulfone, Z-methylallyl octadecylsulfoxide, crotonyl nonadecyl carbonate, etc., including the fluorinesubstituted derivative of these compounds wherein one or more hydrogenatoms are substituted for the fluorine atom, for example, fluorovinyldodecyl ether, 2 fluoroallyl octadecyl sulfide, fluorocrotonyl tricosylcarbonate, Z-fiu-oromethylallyl eicosyl ketone, fiuoroviny-ltetrafluor-otricosyl sulfone, Z-fluoroallyl hexafluorotriaconty-lsulf-oxide, hexadecyl trifiuoroacrylate, tetradecyl fluoromethacrylate,2-fluoroallyl myristate, etc.

Because of the ready availability of raw materials and ease ofsynthesis, and the suitability and outstanding properties as lubricantsand as additives to other well known lubricants, we prefer to use thevinyl, allyl and crotonyl esters of the saturated fatty acids (linearallyl carboxylic acids) having from 11 to 24 carbon atoms in the alkylgroups of the carboxylic acid, or crot-onic acid esters of linear alkylalcohols having from 11 to 24 carbon atoms.

All of the above materials may be used alone, mixed with each other, ormixed with other well known lubricants, for example, mineral oils oflubricating viscosity,

greases made from such lubricating oils, silicone lubricab.

ing oils, diester lubricating oils, etc.

When one solid surface moves relative to another surface with alubricant between the two surfaces, there may be a complete film oflubricant separating the two surfaces or there may be varying degrees ofsolid to solid Contact. The former condition exists under idealhydrodynamic lubrication while the latter condition is characteristic ofboundary lubrication. Complete hydrodynamic lubrication may be obtainedunder certain ideal conditions found in bearings but is influenced bysuch factors as design of the two solid surfaces, load on the surfaces,and the relative speed of the one part to the other. However, even underthese conditions, boundary lubricating problems are encountered duringstopping and starting operations and, from a practical standpointperfect hyrodynamic lubrication is approached rather than attained.Therefore, the ability to improve boundary lubrication is to be greatlydesired.

Our compositions improve the lubrication of two solid surfaces movingrelative to each other especially when one of these surfaces is a metalused for fabricating structural shapes, e.g., iron, molybdenum, silver,copper, beryllium, tungsten, magnesium, titanium, zirconium, chromium,nickel, cobalt, aluminum, tin, etc., and various metal compositions, forexample alloys, of which typical examples are steels, brasses, thevarious alloys of magnesium, cobalt, zinc, zirconium, beryllium,aluminum, iron (e.g., stainless steels), etc. The other surface may bethe same or a different metal or it may be another solid material, e.g.,wood, molded synthetic resins, laminates, etc., or a special compoundedcomposition such as porous metal, graphite, graphite impregnated metal,soft bearing alloys, e.g., babbitts, etc., or very hard compositions,e.g., metal carbides, nitrides, etc.

Normally, in the design of equipment where one solid surface movesrelative to another, both solid surfaces are the same material if thewear is to be equal on both parts or one is made of a material softerthan the other when the wear is to be essentially all on the softerpart. This 6 is usually done when one part is easier to replace than theother or the one part is being cut or shaped by the other.

A concentration of as little as 0.1% by weight of our compositions inanother lubricant improves the boundary lubricating properties of thesematerials, but we have found that for a solid surface of aluminum or ametal composition containing at least aluminum, such as an alloy ofaluminum (hereinafter all these aluminum materials being referred to asaluminum composition), moving relative to another solid surface of analuminum composition, or another metal, the ooefiicient of frictionsuddenly decreases by a considerable amount when the amount of ourmonomeric compound is at least 10% by Weight of the total lubricant.This discovery permits the use of a wide variety of aluminumcompositions for the first time in the fabrication of bearings and likesurfaces, since, as far as we are aware, prior to our invention, no waywas known to prevent galling and seizing of bearings made of many ofthese materials. Although specific alloys of aluminum were made forbearings, the use of such compositions required concessions to be madeas to hearing clearances, life, etc., in order to provide adequateperformance.

For other lubricating applications, especially where metals harder thansoft aluminum are used, concentrations of less than 10% by weight of ourmonomeric, olefinic compounds have been found to be useful. For example,in the lubrication of a steel journal in a die cast aluminum hearing ora stainless steel journal in a babbitt bearings, mineral lubricatingoils containing concentrations of 2-7% by weight of the monomeric,olefini-c compounds have been found to be very effective lubricants,whereas the same mineral lubricants without our additives were not asatisfacory lubricant for these applications.

Likewise, our monomeric compounds, or mixtures thereof, permit aluminumcompositions to be shaped, for example, by drawing, spinning, extrusion,and the like, with a very smooth finish. When our materials are used asthe lubricant without dilution for extrusion or drawing, the aluminumcomposition is formed with a very smooth, mirror-like finish which isimpossible to obtain by the use of any previously known lubricant.Typical examples of the various aluminum compositions that may belubricated by our monomeric compounds are those disclosed on pages851-853 and 865958 of Metals Handbook, volume 1, Properties andSelection of Metals, American Society for Metals, Novelty, Ohio, eighthedition, 1961, for example, the high purity aluminum alloys which aregreater than 99% aluminum, e.g., EC alloy, 1060 alloy, 1100 alloy, etc.,and alloys of aluminum with other metals, for example, copper, silicon,magnesium, tin, zinc, etc., as are more fully described on pages 955958of the above reference.

Typical of the mineral or hydrocarbon oils of lubricating viscosity arethe hydrocarbon lubricants obtained from petroleum. These productsnormally have viscositics in the range of 25 to 10,000 Saybold UniversalSeconds (S.U.S.), and may be a single mixture of hydrocarbons.

Typical of the silicone lubricating oils are those disclosed in, forexample, US. 2,4l0,346-Hyde; 2,456,- 496Ford et al.; 2,469,888 Patnode;2,469,890Patnode; 2,970,162-Brown; etc.

Typical of the diester and polyester lubricants are those disclosed inU.S. 2,450,221-Ashburn et al.; 2,450,222-Ashburn et al.; U.S.2,977,301-Bergen et al.; and on pages 1624 of Technical Publication No.77, published by American Society for Testing Materials, Philadelphia,entitled Symposium on Synthetic Lubricants. Other lubricating materials,as well as suitable mixtures of these; lubricating materials, may beused in the practice of our invention without departing from the scopeof the invention.

The compositions of our invention covered by the above general formulavary from liquid to solid materials. The solids when dissolved inlubricating oils are capable of producing fluids and greases havinglubricating properties depending on the composition and concentration.In low concentrations the effect is to lower the viscosity of some ofthe oils.

To aid in obtaining the grease-like consistency desired for lubricatinggrease, non-abrasive fillers such as silica gel, carbon black,diatomaceous earth, molybdenum sulfide, tin sulfide, graphite, etc., maybe added or soaps or other materials may be incorporated to produce agel structure. Particularly useful soaps are the metallic soaps such asthe alkaline or alkaline earth soaps of the fatty acids, but other soapsmay also be used, for example, zinc, tin, lead, copper, etc., soaps ofthe fatty acids. A particularly desirable grease composition may be madefrom lithium stearate and lithium hydroxy stearate. These greasecompositions may be made by any of the well known methods, for example,as disclosed in US. Patent 2,450,22 lAshburn et al.; 2,450,222Ashburn etal.; and 2,260,625Kistler.

We have also prepared satisfactory greases by merely mixing themonomeric compounds, a lubricating oil and a soap at room temperature.In addition, pour depressants, stabilizers, inhibitors, and the like,may be added to our compositions if desired.

The ability of our monomeric olefinic compounds to function aslubricants either alone or as additives to other lubricants is due totheir being present in the monomeric or unpolymerized state. Ourcompounds in which the olefinic moiety is allyl or crotyl do notpolymerize under the conditions encounter'ed in use as lubricants.However, any compounds in which the olefinic moiety is vinyl (includingacrylates and methacrylates) are susceptible to polymerization ifexposed to elevated temperatures for extended periods of time. For thoselubricants containing compounds which can be polymerized, it isnecessary that the latter remain essentially unpolymerized. Thispresents no problem for many applications since at the normal ambienttemperatures encountered in their use as lubricants, there is little ifany tendency for our compositions to polymerize. In general, bearingsare designed so that the temperature of the bearing does not exceed 200F. and preferably l60180 F. If polymerization does occur, there is amarked increase in the viscosity of the lubricant. In carrying out thespecific examples illustrating our invention, we never detected anyviscosity increase of the lubricant.

For those lubricants in which polymerization might occur, especiallywhere the lubricant may be subjected to elevated temperatures, it isdesirable to have a material dissolved in the lubricant which willinhibit polymerization. A host of materials are well known in the artwhich will inhibit or retard polymerization. These are generallycompounds which contain one or more of the following groups: nitro,nitroso, quinoid, phenolic hydroxyl, amino, etc. Sulfur andsulfur-containing compounds also can be used. Typical specific examplesare: picric acid, trinitrobenzene, 2,5 -dihydroxy-1,4-benzoquinone,1,4-naphthoquinone, 1,4-benzoquinone, chloranil, 9,10-phenanthroquinone,tert-butylcatechol, 4-amino-1-naphthol, hydroquinone,phenyl-fl-naphthylamine, triphenyl phosphite, nitrodimethylaniline,hydroxydimethylaniline, nitrosodimethylaniline, sulfur,paraformaldehyde, phenylacetylene, the condensation products ofaliphatic aldehydes with aromatic amines, etc.

The choice and amount used is dependent on the particular desires of theuser and the properties desired in the lubricant. In general, it shouldbe one that is soluble in the lubricant, is compatible with otheringredients and will not deleteriously affect the lubricant or thelubricated parts. Generally, a small but effective amount, sufiicient tostabilize the composition against polymerization during use, should beused. Such an amount is known as a stabilizing amount.

The ability of inhibitors and retarders to prevent polymerization variesbetween the particular compounds. In

general, those compounds known as inhibitors are more effective inpreventing polymerization than retarders, but the latter are effectiveif used in amounts larger than normally used with inhibitors. Somecompounds, for example the quinones, act as both inhibitors andretarders. These properties of inhibitors and retarders are well knownand are discussed in detail in many books on polymerization. When eitheran inhibitor or retarder are used in amounts to essentially preventpolymerization, they are called stabilizers or polymerizationstabilizers. Generally, amounts from 0.01 to 5% by weight of thepolymerizable material are effective amounts to stabilize thecompositions against polymerization.

In preparing a lubricant in which one or more of the monomeric, olefiniccompounds is dissolved in an oil of lubricating viscosity, it may not benecessary to add a polymerization stabilizer even though the monomeric,olefinic compound is one that can be polymerized and the lubricant is tobe used for extended periods of time at elevated temperatures. Such acase would arise if the oil of lubricating viscosity already had amaterial dissolved in it that had been added either as an oxidationinhibitor or other additive, but which also is a polymerizationstabilizer. Such additives are generally used in concentrations from 0.1to 1% by weight of the oil. Therefore, such an amount would besufiicient to stabilize the monomeric, olefinic compound againstpolymerization when it was dissolved in such an oil.

In order that those skilled in the art may better understand how ourinvention may be practiced, the following examples are given by Way ofillustartion, and not by way of limitation. In all of the examples, theolefinic compounds were unpolymerized, i.e., they were monomeric in formand retained the olefinic group, and the percentages are by weight.

Example 1.A billet of commercially pure aluminum (1100 alloy) 1 inch indiameter by 3 inches long was heated to 200 F. and forward extrudedthrough a inch die heated to 260 F. using an extrusion force of 66,000lbs./ square inch. Vinyl stearate was melted onto the surface of thebillet before being placed in the extruder to act as a lubricant. Thealuminum extruded smoothly producing a rod with a smooth, highlypolished mirror finish. When this example was repeated but using an oilcomposition made by dissolving 25% by weight vinyl stearate, 25% byweight ot-hexadecylene and 50% by weight of a mineral lubricating oilhaving a viscosity of 600 S.U.S. (Saybolt Universal Seconds), thealuminum also extruded readily to produce an aluminum rod having asmooth matte finish.

When the example was repeated using a commercially available lubricantrecommended for extrusion of aluminum, galling of the surface of the rodwas encountered during the extrusion which caused the surface to bestriated with relatively wide, deep scratches.

Example 2.A round bar of commercially pure aluminum (1100 alloy) 1%inches in diameter Was placed in an engine lathe equipped to measure thecutting force exerted on the tool tip, the radial force exerted on thecutting tool, and the feed force necessary to feed the cutting toolalong the surface of the aluminum. The tool was set to feed at the rateof 10 mils per revolution, the depth of cut was mils, and the speed ofrotation of the test piece was such as to give a surface speed of 10feet per minute. The aluminum had a Brinell hardness of 27.2. Three testcuts were made, one using no lubricant, the second using a commerciallyavailable aluminum cutting fluid, and the third using a 20% by weightsolution of vinyl stearate in a mineral lubricating oil of nominal 300S.U.S. The solution had a nominal viscosity of S.U.S. Table I presentsthe results of the three forces using the three test conditions as Wellmeasured in TAB LE I 10 by means of machine bolt 7 to a base member 5which is restrained from rotation with respect to chamber 6. A reservoirof lubricant 8 under test is maintained around the test pieces. A heater(not shown) is provided in l machine aluminum] 5 the base of chamber 6to permit operation at various temperatures. Chamber 6 rides on a seriesof ball bear- No t cigi nme c iai gg g y ings, one of which is shown as9, which ride upon mem- Lubman mg m sysop ber 10, which forms theuppermost portion of plunger 11, which is connected to a hydraulicsystem (not shown) Cutting 450 230 115 to permit various loadings to beestablished between the Feed 125 two test samples 1 and 2. When rider 1is rotated against g 59 45 test washer 2 by means of clock-wise rotationof shaft 3, chamber 6 will rotate upon member 10 due to the frictionalforce existing between members 1 and 2. The These results Show that thevmyl $teamie '1ubr1cat 1ng force required to prevent such rotation ismeasured by oil solution not only gives a lubricant which requires aStrain gauge attached to arm 12 This difi ti much less cutting force,but also produces a smoother permits the coefficient of friction to becalculated and finish. examination of riders 1 and 2 permits evaluationof the Example 3-A1um1n11m "P 0-075 Inch thlck by 3 amount and type ofwear produced. It is desirable to inches Wide Was h a e to 3 and rolledto have the lower surface of rider 1 in parallel contact with give aTeductlon 1n thlckness to lnch; When a the upper surface of washer 2.This can be obtained Water based, Tonlng lllbflcant 15 use, thealunllnurfl Welds either by machining the rider and washer to closetolto the hard n d Steel 11 HI 1 fesultmg In P erances, or moreconveniently by inserting a resilient rolling and requires frequentstops to clean the roll. pad Shown) betwen h b member 5 and h However,Whin Vinyl 'Steamte Was melted and Ramted top surface of the heater inthe base of chamber 6. onto the cold rolls as lubricant, the a111m 1m1mP W Since this pad must be resistant to oil and heat, it issatisfactorily Sheeted to Produce an alumlnum P With conveniently madeof silicone rubber. This pad not only a smooth finish. permits thewasher 2 and base member 5 to self adjust Example Order to detefmlllethe abihty of our so that the top surface of washer 2 will be inparallel monomeric compounds to satisfactorily lubricate two sur-Contact i h h iower Surface of rider 1 b also faces, on6 movlng felatlvet0 the ether, the following vents base member 5 from rotating on theface of the tests were carried out, using a modified 4-ball wear testheater i ho f t i m c descfibfid, for p 111 an article y Using thisapparatus, the following measurements were Larson, entitled Study ofLubrication Using Four-Ball made Th id ith a fl t annular area f 0393Type Machine, Lubrlca o Englneeflng P 5 square inch was rotated under a10 kilogram load at August 1945. This machine was modified by r nl g0.88 r.p.m. (surface speed of 0.0461 inch per second) the f r b21115 andtheir holder With 3 P and Wash against the test washer. These conditionsrepresent opas shown in FIG. 1. Rider 1, made of one of the meterationin the bondary friction region, the most diffil to be investigated, iscup-shaped and is rotated at cult condition of bearing operation from alubrication preselected speeds against stationary test washer 2 madestandpoint. The composition of the test pieces, the of the same ordifferent metal to be tested, by means lubricant, and the resultsobtained are given in Table of motor driven shaft 3 to which rider 1 iattached II. All percentages are by weight, and the tests were run bymachine bolts 4 and 4. Washer 2 is rigidly fastened at room temperatureunless otherwise noted.

TABLE II Average Lubricant Rider Washer Cocfiicient Wear Surface oiFriction Plionyl vinyl ether 1100 aluminum 1100 aluminum 0. 5 Galledafter few seconds or forced running. N-allyl aniline 0. 5 D0. Diallylazelate 0. 5 Do. Allyl stearate... 0. 12 Very little wear after 1 hr.Hexadecyl croto 0. 10 No visible wear after 1 hr. Vinyl stcarate 0. 10Very little wear after 1 hr. 20% vinyl stcarate, 0 0.12 Do.

(150 8.17.5. lubricating oil). 20% methyl stearate, 80% SAE-IO spindle0. 22 Badly gallcd surface after 1 hr.

oil. Vinyl stcarate (tested at 110 F.) Ha dened steel, -62 Aluminumalloy 43 0.12 Highly polished 1-2 micro inch finish, Rockwell. 5% weartrack 20-30 micro inch deep aftcr3hrs. Do 1100 aluminum 1100 aluminum"0.1 Slight wear track after3 hrs. 47% vinyl stcarate, 53% GAE-10 spindleoil. Hardened steel, 60-62 Aluminum alloy 0.17 Highly polished 1'2 microinch finish, Rockwell. igvgar track 20-30 micro inch deep after TS. Coldrolled steel, do 0. 12 Polished wear track in 3 hrs.

10-12 Rockwell. o 1100 aluminum" 0.12 Do. 1100 aluminum o 0.12 Slightwear track in 3 hrs.

Cold rolled steel Aluminum alloy 0.29 Wear track grooved; gelled areasduring3 60-62 Rockwell. hr. test. de 1l00a1uminum 0.29 Do. do Coldrolled steel 10-12 0. 18 Slight wear track in 1 hr.

Rockwell. 20%1 vinyl stearate, SAE-10 spindle ,do do 0.12 Do.

01 SAE-IO spindle oil d0 Magnesium 0.24 Deep wear track inl hr. 20%vinyl stearate, 80% SAID-10 spindle do ..d0 0.20 Slight wear track in 1in.

oil. SAE-lO spindle oil Copper Copper 0.40 Galled badly inlhr, run. 20%vinyl stearate, 80% SAE-IO spindle do do 0.21 Slight wear track,

oil. SAE-10 spindle oil Titanium Titanium 0.56 0.68 Badly galled andgrooved during 1 hr,

run. 20% vinyl stearate, 80% SAE-lO spindle .d0 -do 0.31 Slight Weartrack.

oil.

Sec footnotes at end of table.

il l

TABLE IICntinued Average Lubricant Rider Washer Coefficient Wear Surfaceof Friction SAE-lO spindle oil Phenolic laminatc Aluminum alloy 43 2Polished track.

25% SAID-l0 spindle oil, 75% vinyl stearate. d do Do Octyl acrylateDecyl acrylate Do dccyl acrylate Octadecyl acrylate (run at 95 F.)

Gallcd in 30 minutes.

Grooved wear track in 30 minutes.

Polished wear track in 30 minutes;

slight grooves in 60 minutes.

Slight wear in 30 minutes.

Phcnyl ethyl acrylate 68 Seized in 5 minutes, badly galled. 2-butoxyethyl acrylate 0. 68 Seized in 2 minutes, badly galled. Decylmethacrylate 0. 68 Badly galled during 30 minute test. Dodecylmethacrylatc 0. 17 Slight groove after 30 minutes. Ally] benzoate 0. 68Seized in 2 minutes; badly gelled. Allyl pelargonate 1 0.32 0.68 Badlygelled during 30 minute test. Allyl palmltate 0. l6 Slight wear after 30minutes. Silicone lubricating oi l 0. 2 0. 68 Galled during 1 hr. test.20%lginyl stcarate, 80% silicone lubricating O. 13 Polished track after1 hr.

01 12.94% vinyl stearate, 51.76% mineral lub- 0. Very slight wear after1 hr.

ricating oil (300 S.U.S.), 35.30% lithium hydroxy stearate. 26% vinylstearate, 39% mineral lubricating 0. 08 Slight wear after 1 hr.

oil (300 S.U.S.), 35% lithium hydroxy stearate. 10% vinyl stcarate, 10%dodecyl acrylate, 0.13 Do.

80% mineral lubricating oil (150 S.U.S). 13% vinyl stearatc, 52% minerallubricating do 0. O7 Polished track; no wear evident after oil (300S.U.S.), 35% lithium stearate. 1 hr. 5% vinyl stearate, 95% SAE-IO oilMachine steel Die east aluminurrn-.. 0.14 lrolisllged1 track; slightwear after 3 hrs.

g. 0a 26% vinyl stearate, 39% mineral lubricat- 1100 aluminum 1100aluminum 0.08 Polished track; no wear evident after ing oil (300S.U.S.), 35% lithium stearate.

1 Very erratic during entire run. 2 Erratic.

3 Commercially available methyl phenylpolysiloxane fluid containing 50mole percent silicombonded phenyl groups and 50 mole percent siliconbonded methyl groups.

Example 5.The apparatu described in Example 4 was used to measure thecoefiicient of friction of various percentage compositions of vinylstearate in SAE-lO spindle oil. The rider and test washed were both madefrom aluminum. The results are shown in Table III.

TABLE III Average coefficient of friction 0 (erratic) 0.40

Example 6.Standard production /3 H.P. motors having a normal speed of1,725 r.p.m. were made with the only modification being as illustratedin FIGURES 2 and 3. Generally, the bearing 20 is made by machining shafthole 21 to a size which permits a steel babbitted bearing to be pressedint-o place. This bearing is machined to fit shaft 22 with the necessaryclearance. Cylindrical oil felt 23 has three fingers 24-, one of whichis shown in FIG. 2, which protrude from slots 25a, 25b and 250. Oil isadded to oil hole 26 and is fed through felt 23 to shaft 22. Any oilcreeping along the shaft is thrown off by slinger rings 27 and 27'. Asimilar bearing is at the opposite end of the motor. One motor was madein the usual way with a babbitted bearing at each end of the motor. Fourother motors were made; in each case, the bell housing 23 was cast inone piece with the diameter of hole 21 as cast being slightly smallerthan the diameter of shaft 22 to permit machining and finishing of thebearing surface with nominal bearing clearance. The bell housing wascast from aluminum alloy 43 containing 95% aluminum, 5% silicon. Themotor with the babbitted bearings and one motor with the machinedaluminum bearing were lubricated with the mineral hydrocarbon oil havinga nominal viscosity of 150 S.U.S. recommended by the manufacturer forlubrication of the standard motor. The other three motors werelubricated with the same type of hydrocarbon oil but containing 20% byweight vinyl stcarate. Although vinyl stearate is a solid material atroom temperature, it lowers the viscosity of a hydrocarbon oil when itis dissolved. In order to eliminate any effect of viscosity, the vinylstearate Was dissolved in a hydrocarbon oil having a nominal viscosityof 300 S.U.S., which gave the resulting solution a nominal viscosity ofS.U.S., the same viscosity as the oil Without vinyl stearate used tolubricate the other two motors. A weight was suspended through a ballbearing On the end of the shaft of the motor with the babbitted bearingsand one of the motors containing the machined aluminum bearingslubricated with the vinyl stearate-hydrocarbon oil lubricant compositionto give a bearing pressure in each motor of 147 lbs/square inch. Theother three motors had a bearing pressure of 5'lbs./square inch. The twomotors with the high hearing pressure and one of the other motorslubricated with the vinyl stearatc hydrocarbon oil composition wereplaced on cyclic operation where they ran for 30' minutes and were offfor 10 minutes. The other two motors were placed on continuou operation.After 2 minutes of operation, the motor with the machined aluminumbearings lubricated with a straight hydrocarbon oil failed due toseizure of the bearings which was so severe that it has been impossibleto free the shaft to permit it to rotate. The other four motors havebeen running for over 13,750 hours with no sign of failure with thethree motors on cyclic operation having made over 20,625 starts andstops.

When two other motors, one with babbitted bearings lubricated withstraight hydrocarbon oil and the second motor containing the machinedaluminum bearings lubricatcd with the 20% vinyl stearate in hydrocarbonoil, were measured for starting friction, it was found that the motorwith babbitted bearings had a starting friction of 8 oz.-ft. when thereis a belt pull of 50 lbs. on the shaft, and a starting friction of 28oz.-ft. when there is a belt pull of 75 lbs. on the shaft. Thesecorresponding values for the machined aluminum bearings lubricated withthe vinyl stearate hydrocarbon oil composition were 3 and 6-oz.-ft.,respectively, illustrating the effectiveness of our materials inreducing the starting friction as well as their ability to lubricate abearing made from a regular aluminum casting alloy.

Example 7.A standard production locomotive axle, made of low carbonsteel, was mounted in an engine lathe and rotated against an M-2 steelfinishing roller using a 50% by weight olution of vinyl stearate inkerosene.

These techniques produced a 3-microinch finish on the rolled surface.

Example 8.-Using the same technique and equipment as in Example 4, analuminum washer and rider, both made of 1100 alloy (commercially purealuminum) were used with the lubricants and results shown in Table IV.Each run was for one hour.

erratic and in 30 minutes was 0.32.

At end of period lubricant replaced by following lubricant.

20% hexadccyl crotonate, In two minutes eoefll- Polished wear 80%octane. cicnt declined from track over 0.32 to 0.13 and ran originalgalled at this low value for area. balance of test. Do 0.12 Polishedwear.

track 20% vinyl stearate, 80% 0.12 Do.

cetane.

In Examples 4, and 8, where the average coefficient of friction is notedas erratic, it is meant that the various readings were quite widelyspread showing a tendency to grab and break loose, which is indicativeof very poor lubrication. It is to be noted that our lubricants did notdisplay this characteristic. Furthermore, Example 8 demonstrates theability of our lubricants to repair the damage caused by a poorlubricant and to then lubricate the damaged surface with almost the sameability as a smooth surface.

Example 9.Vinyl stearate was used as a lubricant on two wire drawingdies, and approximately 5000 feet of aluminum wire (EC aluminum) wasdrawn down from 0.061 to 0.57 and then to 0.051 inch by these dies. Verysmooth, shiny wire was obtained with no evidence of galling, formationof slivers, or striations. 4

Example 10.--About 100 aluminum slugs 1100 alloy 1% x 2 /2" x A" withends on the 1%" dimension coated with vinyl stearate and backwardextruded to form cans 1%" x 2 /2" x 5" x 0.023" wall. The cans had a 3-microinch surface finish which was very bright without buffing. Thevinyl stearate was easily removed with a trichloroethylene vapordegreaser. When similar cans were made using lanolin and zinc stearateas the lubr-icant, the surface finishes were 15 and 8 rnicroinches,respectively.

Example 11.When the apparatus of Example 4 was used but using a load of5 kilograms, a rider made of -12 Rockwell cold rolled steel and a washerof aluminum alloy 48, and a lubricant of 10% vinyl stearate and 90%SAE-lO spindle oil, the average coefficient of friction was 0.24 for a16-hour test period with only a narrow spread in data. At the end of thetest there was only a slight wear track.

When the test was repeated for 2 hours using a 10 kg. load, thecoefficient of friction was 0.14 and the washer had a shiny wear trackand no evidence of grooving or galling. When the vinyl stearateconcentration was reduced to 5% and the load was 10 kg. and also 20 kg,the coefficient of friction was 0.15 and the washer had a shiny weartrack with no evidence of galling and grooving in both cases in a 2 hourtest. When the test was repeated using a 20% concentration of vinylstearate and a 10 kg. load, the coefficient of friction was 0.12 and thewasher had a shiny wear track with no evidence of galling or grooving in4 /2 hours.

Example 12.-An emulsion was made by heating to C., 15 grams of vinylstearate, 1.5 grams of triethanol amine and 2.6 grams stearic acid.After a homogeneous melt was obtained, grams of water, heated to 100 C.were slowly added with vigorous stirring which was coninued until theemulsion had cooled to room temperature. This emulsion was stable anddid not separate on standing. This emulsion was tested in the apparatusdescribed in Example 4 using an aluminum cup and washer. The coefficientof friction was 0.3 at the start and decreased to 0.08 in approximately3 minutes where it remained constant over several hours of running. Onlyvery slight grooving was observed on examination of the washer after therun, which probably occurred in the initial few minutes of the testbefore the pieces became coated with the vinyl stearate.

Example 13.Both aluminum and stainless steel strip 1 inch wide x 10 feetlong and 55 mils thick were roll formed into decorative trim striphaving a U-shaped crosssection /8 inch on the bottom with A inch sidewalls which were then bent into a square 30 inches on edge with 1 inchradius corners. Using commercially available lubricants, it wasnecessary to form the U-shaped cross-section using a soluble oil whichwas then washed from the piece, the piece dipped in bees wax, dried inan oven, and then bent into the square finished piece. Attempts to use asoluble oil for both the forming and bending resulted in distortion atthe corners. When a solution of 30% vinyl stearate in 70% lightpetroleum distillant known as naphtha or Stoddard solvent wassubstituted for the above lubricants, both the roll forming to theU-shaped crosssection and bending to the square final shape could beaccomplished with only the one lubricant without the intermediate steps.

Example 14.-A die was made for drawing 43 mil thick stainless steelstrip into a 4% inch long tube having a 4.5 inch ID. and a Mr inch wideflange at the top, stepwise reduced to a 3.5 inch I.D. at the center anda further step reduction to a 3% inch LD. /2 inch from the bottom with a/8 inch flange at the bottom. None of the commercially available drawinglubricants would permit this part to be fabricated from the die. When asolution of 40% vinyl stearate in one of the above commercialhydrocarbon drawing oils was used as the lubricant, the parts werereadily formed.

Example 15.When attempts were made to substitute a galvanized sheetsteel 90 mils thick for regular steel of the same thickness, in themaking of a motor shell for use under high humidity conditions whereresistance to rusting was necessary, it was found that the commercialhydrocarbon drawing oil which was satisfactory for the regular steel wasincapable of producing parts from the galvanized steel because theywould fracture in the final drawing operation. This motor shell was inthe shape of a cup approximately 6% inches ID. with a inch rim at thetop, 3% inches deep with a back draw in the center of the bottom 1.5inches in diameter and 1 inch deep. When a solution of 40% vinylstearate was made in the same hydrocarbon drawing oil, the motor shellcould be readily drawn from the galvanized steel without fractureoccurring. The dies were then washed with solvent and attempts made touse the straight oil again. Fracturing occurred as before, but waseliminated when the vinyl stearate solution in the oil was substituted.

Example 16.SA-E 430 stainless steel 31 mils thick was drawn to produce acup-shaped part having a 3% inch diameter x inch deep. In this simplepart it was found that using a one draw operation, the lower edge wouldtear with a commercial hydrocarbon drawing oil, but by using a 25%solution of vinyl sterate in the same drawing oil, the drawing could bemade and less pressure was required.

Example 17.In the making of a flywheel from SAE 430 stainless steel,cone-shaped dimples 1 inch in diami eter x /2 inch deep were drawn usinga commercially available hydrocarbon drawing oil. it was found that itrequired 7 drawing operations and 3 anneals to complete the formation ofthe dimple. When a solution of 30% vinyl stearate in the hydrocarbondrawing oil was 1% feed rate of 0.25 g.p.m. A thermocouple was imbeddednear the trailing edge of the babbitt pad.

Various loads could be applied to the babbitted test pad by means of aclevis-rnounted hydraulic cylinder working through a hardened steel ballin a spherical seat in the back Example 20.-The following test unit wasused to evalsteel journal and babbitt bearing. A inch diameter testrotor of high chrome steel (0.20%, 11% Cr, 1% M0, 1% W, 0.25% V), groundto a 16 microinch finish, was supported in oil lubricated sphericalroller bearing pillow blocks. It was belt driven to operate at speeds upto 3600 rpm. A babbitted test specimen consisting of a inch layer of tinbabbitt (84% Sn, 8% Sb, 8% Cu) was centrifugally cased onto a steel pad1 inch wide by 2 inches circumferential length. The inside diameter of:the babbitted pad was 25 mils greater than the rotor diameter tostimulate the clearance between a bearing and journal. Anoil-distributing groove cut in the leading edge of the test pad providedan inlet for the test lubricant which was supplied at 100 F. from a3-gallon ca- O substituted, the number of drawing operations could bereof the test pad. To stimulate the action caused by a duced to 2 withno anneals between the draws. solid Wear particle in the lubricant, asolid A inch di- Example 18.A die cast piece of aluminum was 101-ameter, mild steel cylindrical pin with a small taper on ished on a beltsander. In one case a high viscosity hythe leading and trailing edge ofthe face of the pin condrocarbon oil was used as a lubricant and in theother 10 tacting the rotor, was inserted through a hole in the cencase100% vinyl stearate was used. The high viscosity ter of the test pad.After the test rotor was brought up hydrocarbon oil produced a 4microinch finish, whereas to speed, this pin was forced against therotor by means the vinyl stearate produced a 1 microinch finish. of anAllen-head screw with a 70 tapered end acting on Example 19.Polyvinylstearate has a melting point a 20 angle on the base of the pin. The pinwas forced of 47-48 C., but it so viscous in the molten state thatagainst the rotor by taking a quarter turn of the screw it cannot beused as a lubricant in the same way as vinyl Which provided a pinadvance of approximately 4' mile t stearate which is a very fluid liquidabove its melting produce wear particles of the pin. If failure of thetest point. pad or journal did not occur after five minutes, another Inan attempt to reduce the viscosity, a solution quarter turn was taken onthe screw. This was continued of the polyvinyl stearate was made in SAE10 hydrocar- 20 until failure did occur or the maximum insertionpossible bon lubricating oil using an elevated temperature to ofapproximately 16 mils was attained. Prior to the test, hasten thesolution. When the material was cooled to each pin and screw wascalibrated so that the actual room temperature, the entire mixtureturned to a solid am unt of travel of the pin for each quarter turn ofthe block of waxy yellow material, as contrasted to the liquid screw wasknown. solution obtained with vinyl stearate. Even a 10% so- T rotor Wasbrought p to speed using the timed lution formed a thick grease at roomtemperature. How- 1 1106 h Wn in Ta l V. ever, a run was made to measurethe coefficient of friction TABLE v at 150 F. using the 10% solution,the apparatus described in Example 4 and an aluminum cup and washer. Theco- Time Period, speed Load on Test pm Insertion efficient of frictionwas 0.16 and after 4 hours, examinaminutes Pad, p- Increment tion of thewasher showed that it was badly grooved, with greater than 2 mils ofwear. A 10% solution of vinyl stearate in the same lubricating oil isliquid at room temgi {288 8 perature. In order to make a comparativetest, a grease 15-25 1,800 78 of substantially equivalent consistency tothat of the 10% 51 88 polyvinyl stearate in the oil was made from 10%vinyl -55 3,600 195 stearate, 55% SAE 20 hydrocarbon lubricating oil and38:8? @1383 i3? 35% lithium stearate. This grease, when tested in the-70 3,600 195 .same way as the polyvinyl stearate grease, had a coefii--75 3600 195 cient of friction of 0.07. After four hours, the aluminum40 washer had only a slightly polished wear track with no Tests wereconducted using a standard 150 S.U.S. evidence of grooving or galling.The results of these (measured at 100 F.) hydrocarbon lubricating oilgentests indicate that polyvinyl stearate is definitely not the erallyused for lubrication of turbines. This oil was equivalent of themonomeric vinyl stearate as a lubritested with and without severaladditives at 5% by weight Cant. concentration. The results are shown inTable VI.

TABLE VI Maximum Maximum Babbitt Probe Depth of Temperature, F. AdditiveInsertion Failure Journal Maximum, Scoring,

mils microinches Before Pin During Pin Insert. Insert.

None 10 Yes 400 218 270 Zinc dialkyl thiophosphate 10 Yes 400 187 190Tricresyl phosphateuo 3 Yes... 400 226 262 yl t te 1s No 40 188 210Example 21.Samples of vinyl stearate, vinyl stearate containing 0.5%hydroquinone as a polymerization inhibitor and vinyl stearate containing0.5% hydroquinone as a polymerization inhibitor and 0.5%phenyl-ot-naphthylamine as an oxidation inhibitor were prepared. Samplesof each were heated for minutes at temperatures of and 200 C. At the endof this time the samples of vinyl stearate with no additive which hadbeen heated at 150 and 200 C. were viscous-liquids, whereas the othersamples were still very fluid. After cooling to room temperature, themelting point of each was determined and found to be 34 C., the meltingpoint of the monomeric vinyl stearate, except for the samples of vinylstearate with no additive which had been heated to 150 and 200 C. Theyhad melting points of 44 C. showing that both had polymerized, but theother pacity circulating system using a gear pump to provide a 75samples had not. In other words, vinyl stearate can be used as alubricant with no stabilizer, at temperatures up to 100 C. with nopolymerization occurring over a 90 minute period or at much highertemperatures, if stabilized with a polymerization inhibitor or retarder.

Example 22.Vinyl stearate containing 0.5% hydroquinone and 0.5%phenyl-a-naphthylamine was tested at 115 F. in the apparatus of Example4 using an aluminum washer and rider. Over a period of 7 hours, theaverage coefiicient of friction was very steady at 0.12. The wear trackwas very shiny with only one slightly grooved spot.

This test was repeated except that the temperature was raised from 100to 350 F. over a period of 110 minutes. The initial average coefiicientof friction was 0.15 and decreased only slightly until a temperature of350 F. was reached when it quite rapidly decreased to 0.04 over a periodof ten minutes. After an additional .ten minutes at 350 F., thetemperature was raised to 400 F. but this caused the average coefficientof friction to increase, apparently because of incipient failure of thelubricating film under the severe conditions of boundary lubrication andhigh temperature. The temperature was decreased to 350 F. and held for80 minutes. At the end of this time, the average coefficient of frictionwas 0.057 and the lubricant showed no increase in viscosity nor evidenceof polymerization.

Example 23.--A 10% solution of vinyl stearate and 0.5% hydroquinone inSAE 10 mineral lubricating oil was tested at 300 F. in the apparatus ofExample 4 for 4 hours using an aluminum Washer and rider. During thetest the average coefiicient was 0.10. Because of the high temperatureat which this test was run, some volatile components of the lubricantdistilled from the apparatus and the lubricant became noticeably darkerin color. Infrared analysis of the lubricant before and after testingshowed no evidence of polymer formation, thus showing the effectivenessof the addition of a polymerization stabilizer to the lubricant toprevent polymerization of the vinyl stearate. Similar results wereobtained when 0.5% sulfur was used in place of hydroquinone.

In the appended claims, we use the term solid as an adjective in itsbroad sense to differentiate between solids, liquids, and gases. Theterm solid par-t includes within its meaning those solid bodies whichare hollow, honeycombed, porous, etc., bodies which have a solidsurface.

The above examples have illustrated many of our compositions which maybe utilized as lubricants. Equally good results will be obtained by theutilization of other compositions falling within the broad generalformula. The examples have also illustrated many of the ways that ourcompositions maybe mixed with other materials to provide outstandinglubricants. Other modifications and variations will be readily apparentto those skilled in the art and are included within the meaning of theappended claims.

What we claim as new and desire to secure by Letters Patent of theUnited States is:

1. A lubricant comprising an oil of lubricating viscosity containingdissolved therein at least 0.1 percent by weight of a monoethylenicallyunsaturated compound having the formula where n is one of the integers0, 1, R is a monovalent radical selected from the group consisting ofhydrogen and fluorine, R is a monovalent radical selected from the groupconsisting of hydrogen, fluorine, methyl, monofiuorome-thyl,difiuoromethyl, and trifiuoromethyl, X is a divalent radical selectedfrom the group consisting of and R" is a monovalent radical selectedfrom the group consisting of linear alkyls having from ll-60 carbonatoms, and linear fluoroalkyls having from 11-60 carbon atoms, and apolymerization stabilizer selected from the group consisting ofinhibitors and retarders in an amount effective to inhibitpolymerization of said monoethylenically unsaturated compound.

2. The lubricant of claim 1 wherein the oil of lubricat- -ing viscosityis selected from the group consisting of mineral, silicone and diesterlubricating oils and the monoethylenically unsaturated compound ispresent in a concentration of at least 2% by weight (if the oil.

3. The lubricant of claim 2 wherein the oil is a mineral lubricating oiland the unsaturated compound is an alkyl ester of acrylic acid whereinthe alkyl group is a monovalent, linear alkyl radical having from 11-24carbon atoms.

4. The lubricant of claim 2 wherein the oil is a mineral lubricating oiland the unsaturated compound is a vinyl ester of an alkylmonocar-boxylic acid wherein the alkyl group is a monovalent, linearalkyl radical having from ll-24 carbon atoms.

5. The lubricant of claim 2 wherein the oil is a mineral lubricating oiland the monoethylenically unsaturated compound is vinyl s-tear-ate.

6. The lubricant of claim 2 wherein the oil is a mineral lubricating oiland the monoethylenically unsaturated compound is hexadecyl croton-ate.

7. The lubricant of claim 2 wherein the oil is a mineral lubricating oiland the monoethylenically unsaturated compound is allyl stearate.

8. The lubricant .of claim 2 wherein the oil is a mineral lubricatingoil and the monoet-hylenical ly unsaturated compound is allyl palmitate.

9. The lubricant of claim 2 wherein the oil is a mineral lubricating oiland the monoethylenically unsaturated compound is dodecyl acrylate.

10. The lubricant of claim 2 wherein the oil is a mineral lubricatingoil and the m-onoethylenically unsaturated compound is dodecylmeth'acrylate.

11. The lubricant of claim 2 wherein the oil is a mineral lubricatingoil and the monoethylenieally unsaturated compound is octadecylacrylate.

12. A grease comprising an oil selected from the group consisting ofmineral, silicone and diester lubricating oils containing a thickenerand a monoethylenically unsaturated compound having the formula C at t X1.

where n is one of the integers'O, l, R is a monova lent radical selectedfrom the group consisting of hydrogen and fluorine, R is a monov-atlentradical selected from the group consisting of hydrogen, fluorine,methyl, monofluoromethyl, difluoromethyl, and trifluoromethyl, X is adivalent radical selected from the group consisting of and R" is amonovalent radical selected from the group consisting .of linear alkylshaving from 11-60 carbon atoms, and linear fiuoroalkytls having from11-60 carbon atoms.

13. The grease of claim 12 wherein the oil is a mineral oil, thethickener is lithium stearate, and the unsaturated compound is an alkylester of acrylic acid wherein the alkyl group is (a monovalent, alkylradical having from 1 1- 24 carbon atoms.

14. The lubricating grease in claim 12 wherein the oil is a mineral oil,the thickener is lithium stearate, and

the unsaturated compound is vinyl ester of an alkyl monocarboxylic acidwherein the alkyl group is a monovalent linear alkyl radical having from11-24 carbon atoms.

15. The method of lubricating two solid surfaces between which there isrelative motion, at least one of said surfaces being a metal, whichcomprises effecting relative motion between the two solid surfaces andmaintaining between the two sunfaces while they are moving relative toeach other, a monoethylenically unsaturated compound having the formulaRll I J where n is one of the integers 0, 1, R is a monovalent radicalselected from the group consisting of hydrogen and fluorine, R is amonovalent radical selected from the group consisting of hydrogen,fluorine, methyl, monofluoromethyl, difiuoromethyl, andtrifluorome-thyl, X is a divalent radical selected from the groupconsisting of and R" is a monovalent radical selected from the groupconsisting of linear alkyls having from 11-60 carbon atoms, and linearflu-oroalkyls having fnom 11-60 carbon atoms.

16. The method of claim 15 wherein the lubricant is an aqueous emulsioncontaining at least by Weight of the monoethylenically unsaturatedcompound.

17. The method of claim wherein one of the said solid surfaces is ametal composition containing at least 50% by weight aluminum.

18. The method of claim 15 wherein one of the said solid surfaces isstainless steel and the other said solid surface is babbitt.

19. The method of claim 15 wherein one of the said solid surfaces issteel and the other said solid surfaces is cast aluminum.

20. The method of claim 15 wherein the unsaturated compound is an alkylester of acrylic acid wherein the alkyl group is a monovalent, linearalkyl radical having from ll-24 carbon atoms.

21. The method of claim 15 wherein the unsaturated compound is a vinylester of an alkyl monocarboxylic acid wherein the alkyl group is amonovalent, linear alkyl radical having from 1124 carbon atoms.

22. The process of shaping a metal composition containing at least 50%by Weight aluminum which comprises maintaining a film of lubricantbetween the metal composition and a shaping member and, at the same timesubjecting the metal composition to sufficient force to create relativemotion between said composition and said forming member and to causedisplacement of some of 20 said metal composition with respect to theremainder, said lubricant comprising a monoethylenically unsaturatedcompound having the formula and R" is a monovalent radical selected fromthe group consisting of linear alkyls having from l1-60 carbon, atoms,and linear fluoroalkyls having from 11-60 carbon atoms.

23. The process of claim 22 wherein the lubricant is an aqueous emulsioncontaining at least 10% by weight of the monoethylenically unsaturatedcompound.

24. The process of claim 22 wherein the unsaturated compound is an alkylester of an acrylic acid wherein the alkyl group is a monovalent, linearalkyl radical having from 11-24 carbon atoms.

25. The process of claim 22 wherein the unsaturated compound is a vinylester of an alkyl monocarboxylic acid wherein the alkyl group is amonovalent, linear alkyl radical having from 11-24 carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 2,020,714 11/1935Wulif et a1. 252-56 2,204,597 6/1940 Humphreys et al 25256 2,257,96910/194l Loane et a1 25248.2 2,788,326 4/1957 Bondi et a1 25256 DANIEL E.WYMAN, Primary Examiner. L. G. XIARHOS, Assistant Examiner.

1. A LUBRICANT COMPRISING AN OIL OF LUBRICATING VISCOSITY CONTAININGDISSOLVED THEREIN AT LEAST 0.1 PERCENT BY WEIGHT OF A MONOETHYLENICALLYUNSATURATED COMPOUND HAVING THE FORMULA